JPS63267791A - Cyclic silethynyl polymers and manufacture - Google Patents
Cyclic silethynyl polymers and manufactureInfo
- Publication number
- JPS63267791A JPS63267791A JP63088356A JP8835688A JPS63267791A JP S63267791 A JPS63267791 A JP S63267791A JP 63088356 A JP63088356 A JP 63088356A JP 8835688 A JP8835688 A JP 8835688A JP S63267791 A JPS63267791 A JP S63267791A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cyclic
- sylethynyl
- substituted
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims description 26
- 125000004122 cyclic group Chemical group 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- KJWMTVIARIJFDK-UHFFFAOYSA-N diethynylsilane Chemical class C#C[SiH2]C#C KJWMTVIARIJFDK-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 229920005565 cyclic polymer Polymers 0.000 description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- -1 phenyl or naphthyl Chemical class 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は新規な環状ポリマー類及びこれらの化合物の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel cyclic polymers and methods for making these compounds.
一般式−（ＲｚＳｉＣ：Ｃ） （式中、Ｒは飽和炭化
水素基、エチレン性不飽和炭化水素基または芳香族炭化
水素基である）の反復単位をもつ非環状シルエチニルポ
リマー類は英国特許第９１４，９３５号明ｉ書に記載さ
れており、該明４１ＩＩ書によれば、有記ポリマー類は
オルガノジフルオロシランとアルカリ金属アセチリドを
反応させることにより調製することができる。一般式［
（ＣＨ＝）２ Ｓ ｉ−Ｃ＝Ｃ］３をもつ単環式シルエ
チニルポリマーはケミストリー レタース（Ｃｈｅｍｉ
ｓｔｒｙ Ｌｅｔｔｅｒｓ）、１９８４年、第５９６頁
に報告されている。この生成物はドデカメチル−３，４
，７，８，１１，１２−へキサシラシクロドデカ−１，
５，９−トリエンからのジメチルシリレンの段階抽出に
より得ることができ、５４０°Ｃでの反応では上述の環
状シルエチニル化合物は１１％しか得られないが、６９
０℃での反応では６８％得られる。この反応の出発原料
の調製はそれ自体非常に複雑な反応である。Acyclic sylethynyl polymers having repeating units of the general formula -(RzSiC:C), where R is a saturated hydrocarbon group, an ethylenically unsaturated hydrocarbon group or an aromatic hydrocarbon group, are described in British Patent No. No. 914,935, Book I, and according to Book No. 41 II, the polymers mentioned can be prepared by reacting an organodifluorosilane with an alkali metal acetylide. General formula [
Monocyclic silethynyl polymers with (CH=)2 Si-C=C]3 are
Try Letters), 1984, p. 596. This product is dodecamethyl-3,4
,7,8,11,12-hexasilacyclododeca-1,
It can be obtained by stepwise extraction of dimethylsilylene from 5,9-triene, and the reaction at 540 °C yields only 11% of the above-mentioned cyclic sylethynyl compound, but 69
The reaction at 0°C yields 68%. The preparation of the starting materials for this reaction is itself a very complex reaction.
我々は今最環中に少なくとも４個の珪素原子をもつ環状
シルエチニル化合物を調製できることを見出した。また
、我々は該化合物が比較的低温でさえ高収率で得ること
ができることを見出した。We have now found that it is possible to prepare cyclic sylethynyl compounds having at least 4 silicon atoms in the ring. We have also found that the compounds can be obtained in high yields even at relatively low temperatures.
従って、本発明は一般式（Ｒ２Ｓ ＋ Ｃ＝Ｃ）ｘをも
つ環状シルエチニルポリマーにおいて、個々のＲが水素
原子、炭素原子数１８個までをもつアルキル基、アリー
ル基、アルケニル基、置換アルキル基、置換アリール基
または置換アルケニル基を表し、Ｘが少なくとも４の整
数を表すことを特徴とする環状シルエチニル化合物を提
供するにある。Therefore, the present invention provides a cyclic sylethynyl polymer having the general formula (R2S + C=C) , a substituted aryl group or a substituted alkenyl group, and X represents an integer of at least 4.
本発明の環状シルエチニルポリマーの一般式において、
Ｘは２５まで、またはそれ以上の値をもち、好適には５
または６である。Ｒ置換基は水素、アルキル基例えばメ
チル基、エチル基、ヘキシル基、ドデシル基またはオク
タデシル基、アリール基例えばフェニル基またはナフチ
ル基、アルケニル基例えばビニル基、アルリル基または
へキセニル基、またはハロゲン化アルキル基、トリル基
またはスチリル基のような置換された基であることがで
きる。好適なＲ置換基はアルキル基またはアリール基で
あり、最適にはメチル基またはフェニル基である。ポリ
マーの個々のＲ置換基は他のＲ置換基とは異なるもので
あっても、若干同じものであっても、全て同じものであ
ってもよい。In the general formula of the cyclic sylethynyl polymer of the present invention,
X has a value up to 25 or more, preferably 5
Or 6. R substituents are hydrogen, alkyl groups such as methyl, ethyl, hexyl, dodecyl or octadecyl, aryl groups such as phenyl or naphthyl, alkenyl groups such as vinyl, allyl or hexenyl, or halogenated alkyl groups. It can be a substituted group such as a tolyl group or a styryl group. Preferred R substituents are alkyl or aryl groups, most preferably methyl or phenyl groups. Individual R substituents on the polymer may be different from other R substituents, some of them may be the same, or all of them may be the same.
本発明の環状シルエチニルポリマーはジェチニルシラン
リチウム化合物とジハロシランを反応させることにより
製造することができる。この方法は環状シルエチニルポ
リマー類を高収率で得られる。The cyclic sylethynyl polymer of the present invention can be produced by reacting a jetynylsilane lithium compound and a dihalosilane. This method provides high yields of cyclic sylethynyl polymers.
従って、本発明は（＾）一般式Ｒ２Ｓ ｉ（Ｃ≡Ｃ）２
（式中、個々のＲが水素原子、炭素原子数１８個までを
もつアルキル基、アリール基、アルケニル基、置換アル
キル基、置換アリール基または置換アルケニル基を表す
）の１種または２種以上のジェチニルシラン類のリチウ
ム塩を、（［１）一般式Ｒ’ ２ Ｓ ｉ Ｘ ２ （
式中、個々のＲ′はＲについて規定したものと同意義で
あり、Ｘはハロゲン原子を表す）の１種または２種以上
のジハロシラン類と反応させることからなる一般式（Ｒ
２Ｓ ｉ Ｃ＝ Ｃ） ｘ （式中、個々のＲは上述と
同意義をもち、×は少なくとも４の整数を表す）で表さ
れる環状シルエチニル化合物の製造方法を包含する。Therefore, the present invention has the general formula R2S i (C≡C)2
(In the formula, each R represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a substituted alkyl group, a substituted aryl group, or a substituted alkenyl group having up to 18 carbon atoms). The lithium salt of jetynylsilane is expressed by ([1) general formula R' 2 S i X 2 (
In the formula, each R' has the same meaning as defined for R, and X represents a halogen atom).
2S i C=C) x (wherein each R has the same meaning as above, and x represents an integer of at least 4).
反応剤（Ａ）は一般式Ｒ２Ｓｉ（Ｃ三ＣＬｉＬで表され
る化合物であり、１種または２種以上のジェチニルシラ
ン類とアルキルリチウム化合物例えばブチルリチウムと
を反応させることにより調製することができる。該反応
は上述の成分を混合することにより行なうことができ、
例えばテトラヒドロフラン、芳香族炭化水素、脂肪族炭
化水素よりなる溶媒またはエーテル溶媒の存在下で行な
うことが好ましい、ジェチニルシラン類は例えばテトラ
ヒドロフラン中で一般式Ｒ２Ｓ ｉ ＣＱのジアルキル
ジハロシランとＨＣ”：ＣＭｇ（１！を反応させること
によりそれ自体から得ることができる。The reactant (A) is a compound represented by the general formula R2Si(C3CLiL), and can be prepared by reacting one or more jetynylsilanes with an alkyllithium compound such as butyllithium. The reaction can be carried out by mixing the above components,
For example, it is preferable to carry out the reaction in the presence of a solvent consisting of tetrahydrofuran, an aromatic hydrocarbon, an aliphatic hydrocarbon, or an ether solvent. It can be obtained from itself by reacting 1!.
ジハロシラン反応剤（Ｂ）は既知の物質であり、それら
の多くが工業的に入手できる。ジハロシランはジクロル
シランであるのが好ましい、該シランの他の置換基は水
素、アルキル基例えばメチル基、エチル基、ヘキシル基
、ドデシル基またはオクタデシル基、アリール基例えば
フェニル基またはナフチル基、アルクニル基例えばビニ
ル基、アルリル基またはへキセニル基、またはハロゲン
化アルキル基、トリル基またはスチリル基のような置換
された基であることができる。好適なＲ′置換基はアル
キル基またはアリール基である。最適なジハロシラン類
はジメチルジクロロシラン、ジフェニルジクロロシラン
及びメチルフェニルジクロロシランである。Dihalosilane reactants (B) are known substances, and many of them are commercially available. The dihalosilane is preferably dichlorosilane, the other substituents of the silane being hydrogen, alkyl groups such as methyl, ethyl, hexyl, dodecyl or octadecyl, aryl groups such as phenyl or naphthyl, alknyl groups such as vinyl aryl or hexenyl, or substituted groups such as halogenated alkyl, tolyl or styryl. Suitable R' substituents are alkyl or aryl groups. The dihalosilanes of choice are dimethyldichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane.
この反応は溶媒の存在下で行なうことが好ましい、溶媒
は反応剤（Ａ）の製造に使用する溶媒と同じものであっ
ても、異なるものであってもよく、反応は上述の方法に
従ってジェチニルシラン類のリチウム塩を製造した直後
に行なうのが有利である。This reaction is preferably carried out in the presence of a solvent, which may be the same as or different from the solvent used in the preparation of reactant (A), and the reaction is carried out with jetynylsilane according to the method described above. This is advantageously carried out immediately after the preparation of the lithium salt.
反応剤（Ａ）と反応剤（Ｂ）の間の反応を行なう反応は
臨界的なものではない０反応は環境温度または環境温度
以下の温度または加温下で行なうことができる０反応は
約１５〜３０℃の範囲内の温度で行なうことが好ましい
０本発明方法は反応を環境温度（すなわち約２０℃）で
行なう場合でさえ環状シルエチニルポリマー類の理論値
の９０％またはそれ以上のような高収率を提供すること
ができる。所望であれば、反応時間は加温を使用するこ
とにより短縮することができる。The reaction between reactant (A) and reactant (B) is not critical. The reaction can be carried out at or below ambient temperature or under heating. The reaction is about 15 Preferably carried out at temperatures in the range of ~30°C, the process of the present invention provides cyclic sylethynyl polymers such as 90% or more of the theoretical Can provide high yields. If desired, reaction time can be shortened by using warming.
反応が完了したら、本発明のポリマーを例えばメタノー
ルのようなアルコール中に沈澱させ、次に濾過または溶
媒蒸発することにより反応混合物から回収することがで
きる。Once the reaction is complete, the polymer of the invention can be recovered from the reaction mixture by precipitation in an alcohol, such as methanol, followed by filtration or solvent evaporation.
このようにして得られた環状ポリマーの個々の単位は操
作に使用するシラン類の選択に依存して他の単位と同じ
単位であっても、異なる単位であってもよい１例えば、
ジメチルジェチニルシランのリチウム塩とメチルフェニ
ルジクロロシランの反応は２個のメチル置換基をもつ単
位とメチル置換基及びフェニル置換基をもつ単位をもつ
環状シルエチニルポリマーを得ることができる。しかし
、これらの単位は交互にある必要はなく、置換基の若干
の転位反応が本発明方法の反応中に生ずることがあるこ
とを示すものである。すなわち、所定の試薬を選択する
ことにより、ホモポリマー及びコポリマーの全ての範囲
を製造することができる。The individual units of the cyclic polymer thus obtained may be the same or different from the other units, depending on the choice of silanes used in the operation, e.g.
Reaction of the lithium salt of dimethyljethynylsilane with methylphenyldichlorosilane can yield a cyclic sylethynyl polymer having units with two methyl substituents and units with methyl and phenyl substituents. However, these units do not have to be alternating, indicating that some rearrangement reactions of substituents may occur during the reaction of the process of the invention. That is, by selecting a given reagent, a whole range of homopolymers and copolymers can be produced.
このようにして得られたポリマーは環境温度、大気圧（
７６０ｍｍＨｇ）で固体物質である傾向にある。The polymer obtained in this way is grown at ambient temperature and atmospheric pressure (
760 mmHg) and tend to be solid materials.
本発明の環状シルエチニルポリマー類はそれらの電子に
富んだ性質から生ずる有用な光学的及び電子的特性をも
つ、ポリマーは例えば半導体類として、光導電素子とし
て、または導波管技術に使用することができる。アセチ
レン性不飽和結合の存在のために、ポリマーを例えば水
素原子と結合した珪素をもつ化合物との付加反応により
更に反応させることもできる。該化合物は本発明のポリ
マーへ上述のようして結合することができる官能基をも
つものであればよい。The cyclic sylethynyl polymers of the present invention have useful optical and electronic properties resulting from their electron-rich nature; the polymers can be used, for example, as semiconductors, as photoconductive elements, or in waveguide technology. Can be done. Owing to the presence of acetylenically unsaturated bonds, the polymers can also be further reacted, for example by addition reactions with compounds having silicon bonded to hydrogen atoms. The compound may be any compound having a functional group that can be bonded to the polymer of the present invention as described above.
以下に実施例を挙げて本発明を更に説明する。The present invention will be further explained with reference to Examples below.
なお、実施例中「部」及び「％」は全て重量によるもの
であり、Ｍｅはメチル基、Ｖｉはビニル基、Ｂｕはブチ
ル基及びｐｈはフェニル基をそれぞれ示す。In the examples, "parts" and "%" are all based on weight; Me represents a methyl group, Vi represents a vinyl group, Bu represents a butyl group, and pH represents a phenyl group.
鰻１ｊ制
ドライアイスで冷却したテトラヒドロフラン（ｔｂｆ）
１００ ｍｌ中のＲ’ Ｒ２Ｓ ｉ （ＣＥ Ｃ）
２（１２，９ミリモル）の溶液へ、ヘキサン中のＢｕ
Ｌｉの２．９モル溶液９Ｔ＠１を添加した。環境温度で
１時間撹拌後、ｔｈｒ５０ｉｌ中のＲコＲ’−３ｉ−Ｃ
４！ｚ（１２，９ミリモル）を徐々に添加した。溶液を
環境温度で４時間にわたり撹拌し、ｔｈｆを減圧下で留
去した。残渣へトルエン５０ｊ！を添加し、ＬｉＣ１を
炉別した。トルエン溶液を５０Ｏｎ＋１のメタノール中
に注入して白色沈澱を得た。ポリマーを濾過により収集
し、メチノールを用いて洗浄し、次に揮発させた。一般
式
ポリマーが得られた。メタノールで洗浄した後に得られ
たポリマーは末端基によるＮＭＲ（核磁気共！０）信号
を示さず、これは純粋なポリマー類が単離できることを
示すものである。Tetrahydrofuran (tbf) cooled with dry ice
R' R2S i (CE C) in 100 ml
2 (12,9 mmol) in hexane to a solution of Bu
A 2.9 molar solution of Li, 9T@1, was added. After stirring for 1 hour at ambient temperature, RcoR'-3i-C in thr50il
4! z (12.9 mmol) was added slowly. The solution was stirred at ambient temperature for 4 hours and the thf was distilled off under reduced pressure. 50J of toluene to the residue! was added, and LiCl was separated from the furnace. The toluene solution was poured into 50 On+1 methanol to obtain a white precipitate. The polymer was collected by filtration, washed with methanol, and then evaporated. A general formula polymer was obtained. The polymer obtained after washing with methanol showed no NMR signal due to end groups, indicating that pure polymers could be isolated.
例示ポリマー
例示操作を使用することにより得られたポリマーは一般
式
個々の反応におけるＲ１、Ｒ２、Ｒ３、Ｒ４の説明及び
収率を第１表に記載する。環状物質の範囲はｍ＋ｎが４
〜２５の範囲内の値で形成された。Exemplary Polymers Polymers obtained by using the illustrative procedures have general formulas and descriptions of R1, R2, R3, and R4 in individual reactions and yields are listed in Table 1. The range of cyclic substances is m+n = 4
-25.
第−−Ｖ−ｊ！
大」自Ｌ Ｒ’ 鉦 几二 旦杏 」Ｌ坐−
１Ｍｅ Ｍｅ Ｍｅ Ｍｅ ９
５％２ Ｐｈ Ｐｈ Ｐｈ
Ｐｈ ９３％３ Ｍｅ Ｐｈ
Ｍｅ Ｐｈ８５％４ Ｍｅ Ｍｅ
Ｐｈ Ｐｈ ９１ ％５ Ｍ
ｅ Ｍｅ Ｍｅ Ｐｈ８０％６
Ｍｅ Ｐｂ Ｐｈ Ｐｈ９０％
７ Ｍｅ Ｍｅ Ｍｅ ８
８５％８ Ｐｈ Ｐｈ
Ｍｅ Ｈ９０％９ Ｖｉ Ｍｅ
Ｐｂ Ｐｈ９３％１０ Ｖｉ
Ｍｅ Ｐｂ Ｍｅ ８５％化合物は
ＨＰ Ｌ Ｃ（高透過性液体クロマトグラフィー：Ｈｉ
ｇｈ ＰｅｒｍｅａＬｉｏｎ ＬｉｑｕｉｄＣｈｒｏ
ｎａｔｏＨｒａｐｂｙ）、２″Ｓｉ及び”ＣＮＭＲ及び
ＴＧＡ（熱重量分析）により特徴付けられた０個々の実
施例において反応生成物は異なる数の珪素原子をもつ環
状化合物の混合物であった。すなわち、実施例１におい
ては、生成物は２４個までの珪素原子をもつ環状化合物
を含有していた。実施例２の生成物は４〜１９個の珪素
原子をもつ環状生成１勿の混合１勿よりなるものて・あ
った。Chapter--V-j! Large” Self L R’ Gong Rinji Dan An” L seat-
1 Me Me Me Me 9
5%2 Ph Ph Ph
Ph 93%3 Me Ph
Me Ph85%4 Me Me
Ph Ph 91%5M
e Me Me Ph80%6
Me Pb Ph Ph90%
7 Me Me Me 8
85%8 Ph Ph
Me H90%9 Vi Me
Pb Ph93%10 Vi
Me Pb Me 85% compound was analyzed using HPLC (high permeability liquid chromatography: Hi
gh PermeaLion LiquidChro
In the individual examples, the reaction products were mixtures of cyclic compounds with different numbers of silicon atoms. That is, in Example 1, the product contained cyclic compounds with up to 24 silicon atoms. The product of Example 2 consisted of a mixture of cyclic products having 4 to 19 silicon atoms.
Claims (1)
状シル エチニルポリマーにおいて、個々のＲが水素原子、炭素
原子数１８個までをもつアルキル基、アリール基、アル
ケニル基、置換アルキル基、置換アリール基または置換
アルケニル基を表し、ｘが少なくとも４の整数を表すこ
とを特徴とする環状シルエチニル化合物。 ２、ｘが５または６の値をもつ請求項１記載の環状シル
エチニルポリマー。 ３、個々のＲがメチル基またはフェニル基を表す請求項
１または２記載の環状シルエチニルポリマー。 ４、（Ａ）一般式Ｒ＿２Ｓｉ（Ｃ≡Ｃ）＿２（式中、個
々のＲが水素原子、炭素原子数１８個までをもつアルキ
ル基、アリール基、アルケニル基、置換アルキル基、置
換アリール基または置換アルケニル基を表す）の１種ま
たは２種以上のジエチニルシラン類のリチウム塩を、（
Ｂ）一般式Ｒ′＿２ＳｉＸ＿２（式中、個々のＲ′はＲ
について規定したものと同意義であり、Ｘはハロゲン原
子を表す）の１種または２種以上のジハロシラン類と反
応させることからなる一般式▲数式、化学式、表等があ
ります▼（式中、個々のＲは上 述と同意義をもち、ｘは少なくとも４の整数を表す）で
表される環状シルエチニル化合物の製造方法。 ５、反応を１５〜３０℃の範囲の温度で行なう請求項４
記載の方法。 ６、反応が溶媒の存在下で行なわれる請求項４または５
記載の方法。 ７、溶媒がテトラヒドロフランである請求項６記載の方
法。[Claims] 1. A cyclic sylethynyl polymer having the general formula ▲ Numerical formula, chemical formula, table, etc. ▼, in which each R is a hydrogen atom, an alkyl group having up to 18 carbon atoms, an aryl group, or an alkenyl group. A cyclic sylethynyl compound representing a substituted alkyl group, a substituted alkyl group, a substituted aryl group or a substituted alkenyl group, and x represents an integer of at least 4. 2. A cyclic sylethynyl polymer according to claim 1, wherein x has a value of 5 or 6. 3. The cyclic sylethynyl polymer according to claim 1 or 2, wherein each R represents a methyl group or a phenyl group. 4, (A) General formula R_2Si(C≡C)_2 (in the formula, each R is a hydrogen atom, an alkyl group having up to 18 carbon atoms, an aryl group, an alkenyl group, a substituted alkyl group, a substituted aryl group, or lithium salt of one or more diethynylsilanes (representing a substituted alkenyl group),
B) General formula R'_2SiX_2 (in the formula, each R' is R
The general formula consists of reacting with one or more dihalosilanes (where X represents a halogen atom) ▲ There are mathematical formulas, chemical formulas, tables, etc. R has the same meaning as above, and x represents an integer of at least 4). 5.Claim 4, wherein the reaction is carried out at a temperature in the range of 15 to 30°C.
Method described. 6. Claim 4 or 5, wherein the reaction is carried out in the presence of a solvent.
Method described. 7. The method according to claim 6, wherein the solvent is tetrahydrofuran.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878709296A GB8709296D0 (en) | 1987-04-16 | 1987-04-16 | Silethynyl polymers |
| GB8709296 | 1987-04-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63267791A true JPS63267791A (en) | 1988-11-04 |
| JP2654075B2 JP2654075B2 (en) | 1997-09-17 |
Family
ID=10616032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63088356A Expired - Lifetime JP2654075B2 (en) | 1987-04-16 | 1988-04-12 | Method for producing cyclic silethynyl polymer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4866153A (en) |
| JP (1) | JP2654075B2 (en) |
| CA (1) | CA1321598C (en) |
| DE (1) | DE3812619C2 (en) |
| FR (1) | FR2614029B1 (en) |
| GB (2) | GB8709296D0 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2646162B1 (en) * | 1989-04-21 | 1993-01-08 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF POLYSILYLPOLYYNES AND POLYMERS OBTAINED AT THE END OF THIS PROCESS |
| GB2233660A (en) * | 1989-06-22 | 1991-01-16 | Dow Corning | Method of making organosilbutadiyne polymers |
| GB8917329D0 (en) * | 1989-07-28 | 1989-09-13 | Dow Corning | Silethynylsiloxane copolymers and method of making them |
| US5247039A (en) * | 1990-01-08 | 1993-09-21 | Dow Corning Limited | Method of making silethynyl polymers |
| GB9000387D0 (en) * | 1990-01-08 | 1990-03-07 | Dow Corning | Method of making silethynyl polymers |
| US4973723A (en) * | 1990-06-01 | 1990-11-27 | Dow Corning Corporation | Process for preparing silacycloalkanes |
| US4996341A (en) * | 1990-07-05 | 1991-02-26 | Kanegafuchi Chemical Industry Co., Ltd. | Condensed bicyclic disilanylene-acetylene compound and method for preparing the same |
| US5241029A (en) * | 1992-01-07 | 1993-08-31 | Iowa State University Research Foundation, Inc. | Diorganosilacetylene-alt-diorganosilvinylene polymers and a process of preparation |
| DE102006039901A1 (en) * | 2006-08-25 | 2008-02-28 | Renate Marquardt | Novel high-water polyurethanes, processes for their preparation and use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3064028A (en) * | 1959-06-20 | 1962-11-13 | Kali Chemie Ag | New polymeric compounds of organosilicoacetylides and procedures for their production |
| DE1089552B (en) * | 1959-06-20 | 1960-09-22 | Kali Chemie Ag | Process for the preparation of novel polymeric organosilicon acetylides |
| GB1314531A (en) * | 1969-07-30 | 1973-04-26 | Dow Corning Ltd | Organosilicon compounds |
| US4719273A (en) * | 1985-09-04 | 1988-01-12 | Massachusetts Institute Of Technology | Method for forming new preceramic polymers containing silicon |
-
1987
- 1987-04-16 GB GB878709296A patent/GB8709296D0/en active Pending
-
1988
- 1988-03-16 GB GB8806281A patent/GB2204041B/en not_active Expired - Lifetime
- 1988-04-12 JP JP63088356A patent/JP2654075B2/en not_active Expired - Lifetime
- 1988-04-13 FR FR8804878A patent/FR2614029B1/en not_active Expired - Lifetime
- 1988-04-14 CA CA000564092A patent/CA1321598C/en not_active Expired - Fee Related
- 1988-04-15 DE DE3812619A patent/DE3812619C2/en not_active Expired - Fee Related
-
1989
- 1989-01-09 US US07/295,703 patent/US4866153A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB8806281D0 (en) | 1988-04-13 |
| DE3812619A1 (en) | 1988-10-27 |
| JP2654075B2 (en) | 1997-09-17 |
| DE3812619C2 (en) | 1997-05-07 |
| GB2204041A (en) | 1988-11-02 |
| US4866153A (en) | 1989-09-12 |
| CA1321598C (en) | 1993-08-24 |
| GB8709296D0 (en) | 1987-05-20 |
| FR2614029B1 (en) | 1990-12-21 |
| GB2204041B (en) | 1991-02-13 |
| FR2614029A1 (en) | 1988-10-21 |
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